Sulfonamido disazo dye



rials.

Patented Sept. 7, 1948 SULFONAMIDO DISAZO DYE Charles F. H. Allen, Charles V. Wilson, and Gor don F. Frame, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application December 29, 1945, Serial No. 638,490

This invention relates to azo compounds having the general formula:

Q and Q each represent a member selected from the group consisting of a single benzene nucleus and a single naphthalene nucleus, and C and C each represent the residue of a coupling component selected from the group consisting of a benzene coupling component, a naphthalene coupling component and a tetrahydroquinoline coupling component. We have discovered that the azo compounds having the'above formula are, depending upon their particular structure, dyes for W001, organic derivatives of cellulose and cotton textilemate- It is accordingly an object of our invention to provide :azo compounds which are suitable for the coloration of wool, organic derivatives of cellulose and cotton textile materials. Another object is to provide colored wool, organic derivati'ves. of cellulose and cotton textile materials of good fastness properties. A further object is to provide a satisfactory method for the preparation of the azo compounds of the invention.

The azo compounds of our invention can be prepared by diazotizing an amine oi the formula:

II and O wherein A, Q, Q, R, R, X and K have the meanin previously assigned to them and coupling the diazonium compound obtained with a benzene coupling component, a naphthalene coupling component or a tetrahydroquinoline coupling component. The diazonium compound can be coupled with two different coupling components or two proportions of the same coupling component. Where two coupling components are emplayed the amine is monodiazotized and coupled with one of the coupling components following which it is again diazotized and coupled with the second coupling component. Where only one coupling component is employed, the amine is normallytetrazotized and coupled with two gram molecular equivalent Weights of the coupling component in one operation.

Coupling components that can be employed in the preparation of the azo compounds of our in- 1 Claim. (01. zen-178p vention include, for example, l-hydroxyn'aphthalene-5-sulfonic acid, 2-hydroxynaphthalene-7- sulfonic acid, 2hydroxynaphthalene-G,8=disulionic acid-,- 1-hydroxynaphthalene-3,6-disulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-amiho-5-hydroXynaplithalene- 7-sulfonic acid, .'1-amino-8-hydroxynaphthalene 3,6- disulfonic acid,- 1-acetamino-B hydroxynaphthalene- 3,6 disulfonic acid, 2 benzamido 5- hydroxynaphthalene-T-sulfonit: acid, l-hydroxyriaphthalenel-sulionic acid, l -amino-8-hydroxynaphthalene-ZA-disulfonic acid, Z-amino-B-hydroxynaphthalene-3,6-disulfonic acid, 2-hydroxynaphthalen-e-3, 6-disulfonic acid, 1,8--dihydr-oxynaphthalene-3,6-disulfonic acid, 1-hydroxynaphthalene-3,8-disulfonic acid, N p hydroxyethyl-a-. naphthylamine, N-fly -dihydroxypropyl-a-naphthylamine, B-hydroxy-1-N-B,Y-dihydroxypropylaminon'ap'hthalene, 5 -'hydroxy-1-N- 3'-hydroxyethyl-aminonaplithal'ene, S-hydroxY-l-N-dy-dihydroxypropylaminonaphthalene, 1 amino 5 naphthol, "N-ethyl-N-fl-hydroxyethylaniline, N- d'y-dihydroxypropylaniline, N-y-hydroxypropylaniline, N-fi-hydroxyethyl-m-toluidine, N,N-di- 8 hydroxyethylanilin'e, N [i hvdroxypropyl 2 methoxy-5-methylaniline, N-methyl-N-p;y-dihydroxypropybm-chloroaniline, N-4,5- dihydroxyn-amylaniline, N-deltahydroxybutyl-m-anisidine, p-cresol, m-cresol, 4-acetamino-Z-Bfl-dihydroxypropylaminoanisole, 1 5 dihydroxypropyltetrahydroquinoline, 1.43,y-dihydroxypropylflmeth .yltetrahydtoquinoline; 1-B-hydroxyethyltetrahy.- 'droqu-i-r'i'oli ne, l-,8; 1dihydroxypropyl-2,7dimeth yltetrahydroquinoline, l- 5 hydroxypropyl- 2-4.- methyltetra'hydroquinol-ine, l-y-hydroxypropyl- 7-chlorotetrahydroquinoline, 1-:(4,5dihydroxy -namy l) tetraliydroquinoline, l-fi -dihydroxyprop- 'iyl-l-acetylaminotetrahydroquinoline and 1-5 dihydroxypropyl-5 acetylaminotetrahydroquino line.

Amine compounds that can be employed in the preparation of the azo compounds of our invention include, for example:

(2) N,N-di-(ii-aminobenzenesulfonyl)-N,N'-dimethyl-p phenylenedlamiiie om em o 0 0 0 I NE: NH:

3) N,N -di-(4-aminobenzenesu1fonyl)-N,N-dimethy1-p-pheuylenediamine '(4) N,N-di-( i-aminophenoxyacetyl)-N,N-dimethyl-p-phenylencdiamine) ene amine (7) N,N-di-(l-amino--naphtholenesulfonyl)-N,N-dimethyl-pphenylenediamine (8) N,N-di-[4-(4-aminobenzamido)-benzoyl]-N,N-dimethyl-pphenylenediamine H (3H3 (1311a O O O HzN- (l0) N,N -di-(1-amino-4-naphthalenesulfonyl)-N,N -dimethyl-pphenylenediamine (ll) N,N-di-(i-amino-B-suliobenzoyl)-N,N-dimetl1yl-p-phenylenediamine It is to be noted that the amines have been numbered for purposes of simplification and will, at times, :be referred to hereinafter by number. Thus, for example, amine 1 refers to N,N-di-(4- aminobenzoyl) N,N dimethyl-p -phenylenediamine and it will be understood that this amine is meant when reference is made to amine 1.

The following examples illustrate the azo compounds of our invention and their manner of preparation. Parts are expressed as parts by weight.

Example 1 tion of sodium acetate in water is slowly added until coupling begins, and coupling is continued for several hours at room temperature. The reaction mixture is then made slightly alkaline with sodium hydroxide and the precipitated red dye is recovered by filtration and dried. The dye compound obtained has the formula:

(EH3 3 I. r

N O H It dyes cellulose acetate rayon rose colored shades.

Example 2 10 parts of N,Ndi-(4-aminobenzoyl)-N,N'- dimethyl-p-phenylenediamine are added to parts of water and 20 parts of hydrochloric acid (sp. g1. 1.19) and diazotized at a temperature of 5-10 C. by the addition of 3.8 parts of sodium nitrite dissolved in water. The reaction mixture is stirred at 5-10 C. for thirty minutes.

One-fourth of the diazomum mixture prepared as described above is added to a solution of 3.6 parts of l-hydroxynaphthalene-e-sulfonic acid (NW acid) in 25 parts of water and 5 parts of 40% sodium hydroxide. The coupling reaction which takes place is allowed to proceed for three hours after which the dye compound formed is salted out by adding sodium chloride. It is purified by dissolving in water and again salting out With sodium chloride. The dye compound obtained has in its free acid form the formula:

A yield of 3.6 parts is obtained. It dyes Wool a light scarlet shade.

Example 3 To a solution of 5.5 parts of l-amino-B-naphthol-ZA-disulfonic acid (2S acid) in 50 parts of water and 5 parts of 40% sodium hydroxide is added /4 of the diazonium solution formed in Example 2. The coupling reaction which takes place is allowed to proceed for three hours. The dye compound formed is obtained by evaporating the reaction mixture to dryness and extracting the residue with methanol. Four parts of the dye compound are recovered from the methanol extract upon removal of the methanol. The dye par oompoundl obtainedlhaaimits free acidvth'e formula: j

SOsH' It. dxeszwoolzblue-red (magenta); shades; By;t-he ub i utionixen ui a n cul -w ht f zeemmqe mydrox neehthale 6-: s f1om. cid: R ac d? r S da r re q nei wnr ole n 11583 e ound; ta ned: ich colorswoolih ownisheredshades. CQuPIXHQ iS hC; lieyegl; to occur. in the flepositionofhthe. naphtha; lene nucleus. Similat-1y, if:an q ivalent;linoleou. lar weight of 1-acetamino-8-hydroxynaphthalene-3,6-disu1fonic acid -(acetyl H acid) is substitutedfor, 2S acid in the foregoing example, adisazo dye compound .is obtained which: colors" wool lilili'shfered shades. Coupling is believed'tooccur in the Z-position of 'thewnaphthalene. nucleus;

Exempted Qne fourth. ofthe ,diazonium solution prepared in Example 2is added to asolutlonpof4i9 partsof"2=hydroxynaphtha1ene-3;6+disulfonic aclcti (R acid) in 35,;parts. ofwater. andg5 parts of 40% aqueous sodium hydroxide solution. The dye pjecipitates as it is formed. ItLis purified 'by'dis solyi'ng in.w ater and salting out with sodium chloride f 'om a, dilute solution. The dye com poundj obtained has in its free *acid f rm the for mula:

Itdyeswool a'brilliant scarlet which isgsomewliat m es han h e g. obtaine w th? e of Example 2;

Example 5 m mixtune; of .4 partsof- N-,N'-di (baminobene, zoyl N d met yl p: phenylenedlaminee. 40: parts of water and- 6 parts of hydroohloric acid (sp, gr 1.19); is, diazotiz edfloy treatmentd with; 12 ,3 5 I of; ar waterasolution of ysodiuml n-itrite con taining lzyparts ;of.;-the salt to 100v )QELHZS :of {5011b .011.;

The-diazoniumlsolution obtainedaoove is added 103.88 partsof N ethyl-N s-hydroxyethylaniline;

6i) partsof water and 4-p'arts-;of' hydrochloric aoida.

(sp. g1 ;,1. 19);; Sodium acetate is -theniiaddedquntill c'oupling begins and after coupling forithreelhoursthelmixtllre .has, a-pI-I of 1.5.1 Therrleactionl ture is then :made alkaline with sodium hydroxide and the precipitated'yellow'dye is collected on a. filter, washed-with, water. and. dried... The il arzo dim compound. obtaineddyes cellulose acetate yele low shades. Coupling-occurs in p positiontothe nitrogen, at om of the coupling; component.

Example 6:: h

1151 parts; of" NJN' -diaflaminobenzenesuh mum-MN e m thy1=p-nh 1 nediamme are diaz otlzedj in parts of water and; 2,3 PB ItSI QfT 6 hyldrpchlonioraoldi (sp; gr: 1219): witle azillpart's of allwssodiummitrite watemsolutiom. Ubonlooms l l I 5. parts ol l'. N,N"-dl-,-(eaminophenoxyacetyll- N;-N"-dlmethyl-pephenylenediamine.l are. di /Z07 tizedjlinl-fiplpartsi of water- ,and. 10. parts of. hydro: chloricacid (sp g r.v 1,19). with-sodiummitrite in theusuallmannerl One-half of, the. diazoniumssolution 5. prepared as, described above i saaddedhtol a isolutioneof'e 3:1 parts... of; khxdrloxypaphthaleneA:sulfenicacid in .351i parts.of.;wa11enand fiipants of. 2.140% aqueous sodi'umhydroxlde solution; The,couplingireacev tion whiolutakesiplaoe ls allowed to=proeeed for3 hours: and-l thearesultingi diazo dye is obtained from: the reaotl'onal-mixture by salting out with sodium-chloride: 1 Gouplingwccurs' in the z-po'sitiomofithe-ooupling component Thedye com pounds. obtained dy esi w'ool a brilliant red shade frmni amaold bath:

Example one ha-lf'of the diazonium solution prepared asdeserlbed mmxam le 7" is'added to a'soliiti'on of 433 f';parts of -l' aminoe8' hydroxynaphthalenee 2i 4 di's ul'fomc '(2Sacidl -in* 35 parts) of water and 5' partsof 40%- aqueous sodium hydroxide solutifoni Thecoupling"reaction which takes place is allowed to proceed fozj"three-hours. The rea'ctionmlx'ture is'then filteredand'the filtrate evap-i oratedtddryne'ssr The residue is'then'extracte'd with methanol and the disa'zodyefis recovered from the methanol. extractby removal of the methanol. Coupling occurs in the 2-position of the,. 2S acid The. dye compound obtained dyes wooLa deep magentacoloriroman aeidbath;

Example-i9; or? part i of: i N,Nj';:a1; 1: amino-2-inaphthoxy acetyl)'N;N"=dimetliyl=p phenylenediamlne are diazotized indiepartsl of water and one part" "of 7 hydrochloric acid (sp. gr. 1.19) with sodiumnitritein the usual manner. The diazonium solution obtained is added to a solution of 0.9 part of 1-amino-8-naphthol-2,4-disulfonic acid (28 acid) in 15 parts of Water and 2 parts of 40% aqueous sodium hydroxide. The coupling reaction which takes place is allowed to proceed for several hours and the mixture resulting is filtered. The filtrate is then evaporated to dryness and extracted with methanol. The disazo dye compound formed is recovered from the methanol extract by removal of the methanol. The dye compound obtained colors wool 'a" reddish-brown shade from an acid bath.

Example 10 2.5 parts of N,N'-di-'-(3-aminobenzenesulfonyl)-N,N'-di-methylp-phenylenediamine are dissolved in a boiling solution of 5' parts of hydrochloric acid (36%) in 25 parts of water. solution is stirred while cooling so that the amine hydrochloride salt precipitates from solution in a finely divided condition. Then ice is added to bring the temperature to about 5 C. and 6.4-par'ts of a 12% aqueous sodium nitrite solution areadd- I The I orange dye formed is isolated by adding sodium chloride and for purification it is salted out twice with sodium chloride from its solution in'water. It dyes Wool orange from an acid bath.

Example 11 Two parts of N,N'-di-(4-aminobenzoyl) -N,N--

dimethyl-p-phenylenediamine are dissolved in 25 parts of water and 3 parts of hydrochloric acid (sp. gr. 1.19) and the resulting solution is cooled with ice to 5 C. Then while stirring, 6.0 parts of 12% sodium nitrite solution are added and stirring is continued for 15 minutes while maintaining the reaction mixture at-about 5 C'; Upon completion of the diazotization reaction the diazonium mixture resulting. is added to asolutionof 0.65 part (1 equivalent) of -2,4-diaminotoluene in 15 parts of water and 1 part ofhydrochloric acid (sp. gr. 1.19) and stirring is continued one and a quarter hours at 5-10 C. Coupling is believed to occur principally in the 5-position. The product formed is recovered by filtration and then added to a'solution of 2.5 parts (1 equivalent) of 2naphthol-3,6-disulfonic acid (R-acid) in parts of water and 2 parts of sodi-. um carbonate and the alkaline solution is stirred for 2 hours at room temperature. The orange dye precipitates out as formed. It is recovered by filtration and dried. It dyes wool an orange color from an acid bath.

Example 12 v I I 1.6 parts of N,N'-di-( l-aminophenoxyacetyl) N,N-dimethyl-p-phenylenediamine are diazo-' IITH:

in 15 parts of water and 0.2 part of sodium carbonate. Then a solution of sodium acetate is slowly added until coupling begins and the reaction mixture is stirred one and a quarter hours at 5-10 0., following which the yellow solution resulting is added to a solution of 0.8'l'part (1 equivalent) of 2naphtho13,6-'disulfonic acid (R- acid') in 20 parts of water and 1.5 parts of sodium carbonate. A red disazo dye begins to precipitate almost immediately and after stirring for about one hour, it is recovered by filtration'and dried. In this manner 4.0 parts of the dye are obtained. It colors wool red shades.-

Example 13 by adding 2.2 parts of a 12% sodium nitrite solu-' tion While keeping the temperature at 510 C. Stirring is continued for 30 minutes. Then the solution resulting is added to a solution of 0.87 part (1 equivalent) of 2-naphthol-3,6-disulfonic acid (R-acid) in 35 parts of water and 2 parts of sodium carbonate. The reaction mixture turns a deeper red in color and a trisazo dye precipitates. After stirring for about one hour, the dye is recovered by filtration. It is purified by dissolving in about 300 parts of hot Water and precipitating by the addition of an equal volume of saturated sodium chloride solution. It dyes wool deep red from an acid bath.

Example 14 0.3 part of N,N-(4-aminobenzoyl)-N,N-dimethyl-p-phenylenediamine are dissolved in 10 parts of water and 0.5 part of hydrochloric acid (sp. gr. 1.19). The reaction mixture is then cooled with ice to 5 C. and diazotized by adding, with stirring, 1.8 parts of a 6% aqueous sodium nitrite solution and the reaction mixture is stirred until diazotization is complete (about 15 minutes).

The diazonium solution prepared as described above is added to a suspension of 0.43 part of 2- ethoxy-l-naphthylamine-6-sulfonic acid in 10 parts of water. While stirring, dilute sodium acetate solution is added to give the reaction mixture a pH of 4.2. The coupling reaction which takes place is continued for 4 hours at 5- 10 C. Coupling is completed by the careful addition of a dilute aqueous sodium hydroxide solution to obtain a pH of 5.3 andfinally a pH of 6.0. A red insoluble disazo dye is formed. It is coagulated by boiling the reaction mixture, and after cooling it is recovered by filtration, Washed with water and dried. It colors wool red shades.

Example 1 5 The dye formed as described in Example 14 is dispersed in 50 parts of water, 0.3 part of a 40% aqueous sodium hydroxide solution are added and then the reaction mixture is heated to boiling and stirred while cooling with ice to 510 C. 1.5 partsof hydrochloric acid (sp. gr. 1.19) are added and the dye is completely diazotized by adding 1.8 parts of a 6% aqueous sodium nitrite solution. The reaction mixture is stirred for one aanaese half .hour at "-10 C. and then added .to'a soluticn :iOf 0.53 :part of 1,8edihydroxynaphthalene- 3j6=disulfonicacid in 25 parts of water and 0.8 part of sodium hydroxide. The reaction 'mixture resulting is stirred for 1 hour andthen allowed to stand overnight at room temperature. The red-brown tetrakisazo dye formed is soluble and is precipitatedby-the addition of an equal volume of a saturated sodium chloride solution. After boiling :to coagulate the dye and coo1ing,.the dye isrecovered by filtration and dried. It dyes wool a .dull red which turns yellow-brown upon chroming.

Similarly by diazotizing both amino groups of the amines listed hereinafter and coupling the diazonium compounds obtained in an alkaline medium with two molecular equivalent weights of the couplingcomponents listed hereinafter in accordance with .the procedure described in the foregoing examples, especially that disclosedin Examples 2, 3, 4, -'7, 8, 9, and 14, disazo dye compounds of our invention can be prepared. The color given is .thatof the dyeing obtained on wool, unless otherwise specified,

Amine Z-hydroxynaphthalenefl-sulfonic acid... '-2-hydroxynaphthalene-6,8-disulfonic acid I l-hydroxynaphthalene-S;6-disulfonic acid 2-an1ino-8-hydroxynaphthalene-S-snlfonic acid f Z-amino-5-hydroxynaphthalcne-7-sulfonic acid r Z-benzaznido-5-hydroxynaphthalene-7-sulfonic acid.

11-amino-B-hydroxynaphthalene-3,fi-disulfonic acid. l-hydroxynaphthaIene B,8-disulfonic acid.

l-amino-8-hydroxynaphthalene-2,4-disulfonic d 1-hydroxynaphthalene--slilfonic acid orange. 4 l-amino-8-hydroxynaphthalene-3,G-disulfonic acid. red.

fi-naphthol Do. 1-an1ino-8-hydro Do. B-naphthol Do,

Coupling Component Color 1,8wdihydroxynaphthalene-3,fi-disulionic acid 2' bluish-red.

L-hydroxynaphthalene-5-sulfonic acid dull organge.

reddish-orange. yellow-orange. reddish-orange. reddish-brown. orange cotton-old reddish-orange cotton reddish -violet.

reddish-orange.

brownish-red.

Likewiseby diazotizing both :amino groups of the amines listed hereinafter and couplin the diazonium compounds obtained in an acid medium with two molecular equivalent weights of the coupling components listed hereinafter inaccordance with the procedure described in the foregoing examples, especially that disclosed in Examples 1, x5, Sand 1.1,-disazo'dye compounds of our invention can be prepared. The color given is that of the dyeing obtained on celluloseacetate rayon.

ethyl N-rp, yadihydroxypropylaniline, -N-dy-dihydroxypropyl l -methy'l 1,2,3;4 tetrahydroquinoline, l-naphtholl-sulfonic acid or 1-amino-58 naphthol-2A-disulfonic acid, amine 9 can bediazotized and coupled with N-ethyl-N whydroxyethyl .m -t0lu idine, -N fin dihydroxypropyl- 1,2,3A tetrahydroquinoline, 5-hydroxy-l-e thyl-v aminonap-litlralene or "1 naphthol 4: sulfohi'c acid, aminelll'canbe diazo'ti'zed and coupled with Coupling Component Color N;N-di-(fl-hydroxyethyl)aniline N-lS,rwdihydroxypropy1-7-n1ethyl-l,2;3,4-tetrahydroquinolinc v 'N-pl-hydroxyethyl-7-incthyl-1,2,3,4-tetrahydroquinoline.

N-ethyl-N-ISHIydroxyethylaniline 5-.hydroxy-l-fi-hydroxyethylamino-naplithalene yellow. red.

Do. yellow. reddish-violet.

It will be understood that the foregoing examples are intended to be illustrative and not limitative of our invention as many other dye compounds included within the scope of our invention not specifically referred to hereinbefore can be prepared. To illustrate amine 1 can be diazotized and coupled with NN-dhB-ihydroxyethyl) -m-toluidine, B-naphtho-l or N-fl/Y-dihydroxypropyl-zfl :dimethyl 1,2,3,4 'tetrahydroquinoline, amine 2*can be diazotized and coupled with o-naphthol, N-Bn-dihydroxypropyl-1,23,4- tetrahydroquinoline, N-ethyl-N- 3-hydroxyethylaniline, ionic acid or I-hydroxynaphthalene-4-sulfonic acid, amine 3 can be diazotized and coupled with 2 amino-B-hydrOXynaphthalene-G -sul-:

tho1-'4=-sulfonic.'acid, 1-amino-=8 naphthol zfi db sultonic acid 'or 5 hydroxy l-fln diliydroxypro pylarninonaphthalene and amine 11 can be tioupled with N-n 'bu-tyl-N- S-hydroxyethylaniline,

* N firr-dihydroxypropyl '7-methyl-1;2,'3; l tetra: hydroquinoline, 1 naphthol--4-snlfonic acid or 5': hydrox-y i -p dihydroxypropylaminonaphtha-' lene, for example. It will be uiiderstood that in forming the disazo dyes referred to above "one molecular equivalent weight of the amine is completely diazotized and coupled with two 'mole'cu lar equivalent weigh-ts of the coupling component.

Disazo dyes of our invention containing two diifierent coupling components can be prepared after, the general procedure described in Example 11. To illustrate, each of amines 1 to 11, inclusive, can be monodiazotized and the diazonium compounds obtained coupled with an equivalent molecular weight of m-toluidine. The resulting monoazo compounds are then diazotized and the diazonium compounds in turn coupled with 1- naphthol-el-sulfonic acid to obtain disazo dye compounds of the invention. Similarly, l-amino- 8-naphthol-2A-disulfonic acid, N-Bn-dihydroxypropyl-7-methyl-1,2,3,4-tetrahydroquinoline or hydroxy l-fixy dihydroxypropylaminonaphthaleneyfor example, can be substituted for the 1- naphthol-4-sulfonic acid. Likewise 2,4-diaminotoluene, 1-amin0-5-naphth0l and u-naphthyh amine, for example, can be substituted for mtoluidine.

The aminobenzene type compounds, such as amines 1, 2, 3, 4, 8, 9 and 11, used in the manufacture of the azo compounds of our invention are prepared by reacting an N,N'-di- (low carbon alkyl group) -phenylenediamine with two molecular equivalent Weights of a nitrobenzoyl halide, a nitrobenzenesulfonylhalide or a nitrophenoxyacetyl halide, as the case may be, and then reducing the nitro groups to amino groups. The aminonaphthalene type compounds, such as amines 5, 6, 7 and 10, can be prepared by reacting an N,N'-di-(1ow carbon alkyl group)-phenylenediamine with two molecular equivalent weights of an acetamino naphthoyl halide, an acetamino naphthalenesulfonyl halide or an acetamino naphthoxyacetyl halide, Representative of the benzene and naphthalene halide compounds that can be used may be mentioned pnitrobenzoyl chlorine, p-nitrophenoxyacetyl chloride, m-nitrobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, m-nitrobenzoyl chloride, 4-(4'-nitrobenzamide) -benzoyl chloride, 4- nitro-2-sulfobenz0yl chloride, 4-nitro 3 sulfobenzoyl chloride, 1 acetamino 2 naphthoxyacetyl chloride, 2-acetamino-3-naphthoyl chloride and 1 acetamino 5 naphthalenesulfonyl chloride.

The followin examples illustrate the manner of preparation of the amine compounds of the invention. Parts are expressed by weight.

Example A. N,N -di-p-aminobenzoyl N,N-dzmethyl-p-phenylenediamine Fifteen parts of N,N-dimethy1-p-phenylenediamine dioxalate were suspended in a solution of 15.7 parts of sodium carbonate in 200 parts of water. Then, while stirring, 29.5 parts of p-nitrobenzoyl chloride were added, and the mixture was stirred first at room temperature for 30 minutes and then at 50-60 C. for 3 hours. On cooling, the precipitated brownish solid was collected on a filter paper, pressed dry, and extracted with 350 parts of boiling ethyl alcohol to remove any unreacted p-nitrobenzoyl chloride or p-nitrobenzoic acid. WOI'king in this manner, 14.2 parts of the crude product N,N'-di-p-nitrobenzoyl- N,N-dimethyl p phenylenediamine were obtained. After recrystallizing from 200 parts of glacial acetic acid a substantiallypure product was obtained in the form of slightly yellow needles which melt at 256 C.

For the reduction to the amino compound, 7.7 parts of the nitro compound obtained above were suspended in 150 parts of ethyl alcohol and reduced with hydrogen at 90-100 C. in the presence of Raney nickel. The reduction took place readily. On cooling, the mixture of amino compound and nickel was filter-ed, and the amino 12 compound was separated by extraction with 150 parts of boiling l/l-diox-ane. On cooling the 1,4- dioxane extraction mixture, 3.7 parts of the product, N,N-di-p-aminobenzoyl-N,N-dimethyl-pphenylenedi'amine, separated in the form of white needles which melt at 255 C.

Example B. N,N-di-m-mltro enzenesulfionyl- N ,N -dimethyZ-p-phenylencdiamine A. From the oxalate-To a solution of 79 par-ts of N,N-dimethyl-p-phenylenediamine oxalate in 1000 parts of water were added parts of so dium carbonate. After foaming subsided, 120 parts of m-hitrobenzenesulfonyl chloride were added, and the mixture resulting was heated on a steam bath with stirring for 3 hours. The reaction mixture became very dark. After cooling, it was filtered and the residue collected onthe filter (167 parts) was washed several times with cold Water and then extracted with 1000 parts of boiling ethyl alcohol. The residue remaining after the ethyl alcohol extraction. was recrystallized from 1,4-dioxane and decolorized with charcoal, 85 parts of material melting at 215217 C. were obtained. The yield Was about 68% of the theoretical, based on the di-amine oxalate.

B. From the free base.-A mixture of 7 parts of N,N--dimethyl-p-phenylene diamine (free base), 25 parts of in-nitro-benzenesulfonyl chloride and 25 parts of sodium carbonate in 200 parts of water was shaken intermittently for V2 hour and then allowed to stand at room temperature for l8 hours. The solid material formed was recovered by filtration, extracted with ethyl alcohol and the residue remaining from the ethyl alcohol extraction was crystallized from acetic acid. 7 parts of the desired product melting at 215216 C. were obtained.

5 parts of the nitro compound obtained above were suspended in 125 parts of 1,4-dioxane and reduced with hydrogen at -100 C. in the presence of Raney nickel. The reduction took place readily. The mixture was heated to the boiling point and filtered while hot. Upon cooling the desired amine compound separated and was recovered by filtration. It melts at 218 C.

Example C. N,N-di-p-amin0phenoryacetyl- N ,N -dimethyZ-p-phenylenediamine To a suspension of 37.2 parts of N,N'-dimethylp-phenylenediamine dioxalate in 500 parts of Water containing 36.6 parts of sodium carbonate, 77.4 parts of p-nitrophenoxyacetyl chloride were added and the resulting mixture was stirred overnight at room temperature, and then for one hour at 50-60 C. On cooling, the dark colored solid which precipitated was recovered by filtration, pressed dry, and recrystallized from glacial acetic acid. In this manner, 22.1 parts of N,N-di-pnitrophenoxyacetyl N,N dimethyl p phenylenediamine were obtained a bull-colored needles which melt at 233 C.

22.1 parts of the nitro compound obtained above were suspended in 400 parts of ethyl alcohol and reduced with hydrogen at 90-100 C. in the presence of Raney nickel. On cooling, the reaction mixture was filtered and the residue obtained on the filter was Washed with parts of boiling 1,4-dioxane to extract the desired product. On cooling the lA-dioxane extraction mixture 6.0 parts of the product, N,N'-di-p-raminoph e-' noxyacetyl N ,N' dimethyl-p-phenylenediamine' were obtained as a slightly yellow solid which melts at 07 C.

13' Example D. 'N,N'all-(1eaminoez-naphthoxyacetyl) -N,N'dimethyZgp-phcnylencdiamine To a mixture of 2.12 parts of N;N-dimethylp-phenylenediamin'e oxalate and iZflparts of sodium carbonate in 50 parts (of water was added 5.0 parts of ;1-nitro-2-naphthoxyacetyl chloride. The resulting mixture was stirred overnight. at room temperature. The precipitated SQlid was recovered by filtration and washed with water; for purification it'was then heated with 50 parts of boiling alcohol and the precipitated solid was recovered by filtrationlafter cooling. In this manner (1.6 parts .of -N,N -.di-(Imitro-Z-naphthoxyacetyl -N,'N- '-dimethylp-phenylenediamine was obtained. Itmelts above 275 C. l

The nitro compound :obtainedas described above was suspendedin 1'20 parts of alcohol land reduced with hydrogen in the presence of Rianey nickel in the customary manner. On concentrating the alcohol solution to a small volume, the desired product separated as buff-colored crystals and was recovered by filtration.

Example E.-N,N-cli--(4-aminobcneeneswlfonyl) N,N'-climethyl-p-phenylenedlamine To a suspension prepared from 29.3 parts of N,N'-dimethyl-p-phenylenediamine in 800 parts of water containing '75 parts of sodium carbonate, 45.7 parts of p-nitrobenZen-esulfonyl chloride were added and the mixture was heated with stirring on the steam bath for two hours. After cooling, the solid which precipitated was recovered by filtration, washed with water and extracted with 400 parts of b0l1ing ethyl alcohol. Upon evapora- I tion of the alcohol N,Ndi-p-nitrobenzenesulfonyl-N,N-dimethyl-p-phenylenediamine is obtained as a light gray solid which melts above 300 C. Working in the manner described 34.3 parts of nitro compound were obtained.

The nitro compound obtained above was reduced to the corresponding amino compound by suspending it in ethyl alcohol and reducing with hydrogen in the presence of R-aney nickel in known fashion. On concentrating the alcohol solution to a small volume after removing the nickel by filtration, the desired product separated as a slightly yellowish solid which melts at 212- 226 C. (decomposes). 7.4 parts of the diamino compound were obtained.

Example F. N,N'-dimethyl-N,N'di- (2-sul,f0-4- aminobenzoyl) pphenylenecliamine 15 parts of N,N-dimethyl-p-phenylenediamine (free base) were added to the aromatic acid chloride (obtained from 21 parts of thiony1 chloride, 300 parts of pyridine and 43 parts of monopotassium salt of 4-nitro-2-sulfobenzoic acid) and the mixture resulting was stirred on the steam bath for 3 hours. On cooling, 18 parts of N,N'- dimethyl N,N' di (2 sulfo 4 nitrobenzoyl)-p-phenylenediamine were separated as a white crystalline compound.

The product obtained above was reduced with hydrogen in the presence of Raney nickel in known fashion with ethyl alcohol as the solvent medium. Upon filtration, to remove the nickel, and evaporation of the filtrate the desired amine compound is obtained as a white solid. It is extremely soluble in water and can be purified by recrystallization from dilute hydrochloric acid. Considerable loss is involved in the purification process.

This compound can be obtained by reacting N,N'-dimethyl-p-pheny1enediarnine with 3-sulfp- 4-nitrobenzoy1 chloride and reducing the nitro compound obtained to the corresponding amine compound. The reactions can be carried out :in accordance with the procedure described in Example F.

Example H -N N '.-d2'- (2-amino-3-naphthoyl) Q N ,N dimetlryl-p-phenylenediamine This compound can be obtained by reacting N,N-dimethyl-p-phenylenediamine with 2-acetaminoeS-naphthoyl: chloride and removing the acetylagroups from the compound thus obtained by hydrolysis; Z-aQQtaiminO-3-naphthoyl chloride can be prepared by acetylating 2-amino-3- naphthalene carboxylic acid to obtain 2-acetamino-3-naphthalene carboxylic acid which is then converted to its acid chloride form (2-acetamino-3-naphthoyl chloride) by treatment, for example, with P015.

Example I .N ,N -tli- (1 -amino-5-naphthalenesaljonyl) -N,N -dimethyl-p-phenylenediamine Example J.-N .N-di-4- (4-aminobenzamido) benzoyl-N,N -climethyl-p-phenylenediamine This compound can be obtained by reacting N,N'-dimethyl-p-phenylenediamine with 4-(4- nitrobenzamido)-benzoyl chloride and reducing the nitro compound obtained to the amine form. The reduction can be carried out with hydrogen in the presence of Raney nickel in the manner hereinbefore described.

Example K .--N ,N -di- (1 -amino-4-naphthalenesuljonyl) -N,N'dimethyl-p-phenylenediamine This compound can be obtained by reacting N',N-dimethyl-p-phenylenediamine with 1-a0etamino-4-naphthalenesulfonyl chloride and removing the acetyl groups from the compound thus obtained by hydrolysis.

The above compound also can be obtained by reacting N,N dimethyl p phenylenediamine with l-nitro-4-naphthalcnesulfonyl chloride and reducing the nitro compound obtained to its amine form. The reactions involved can be carried out in accordance with the procedure hereinbefore described.

It will be understood, as previously indicated, that in Examples A to K, inclusive, at least two molecular equivalent weights of the aromatic halide compound to one of the phenylenediamine compound are employed.

The azo compounds of our invention can be employed for the coloration of the materials named herein by the well-known methods, employed by those skilled in the art, for the coloration of these materials.

2,448,863, 15 16'- We claim: REFERENCES CITED The dlsazo compound havmg the formula The following references are of record in the file of this patent:

CH3 CH3 I l 5 UNITED STATES PATENTS Q SOrNG N Q Number Name Date N 1,878,471 Dobmaier Sept. 20, 1932 OH 011 1,896,450 Lange Feb. 7, 1933 I 1 2,275,130 Clifie et a]. Mar. 3, 1942 FOREIGN PATENTS Number Country Date N OH2CHOH(;H,0H N (}H,QHQHQH,QH 475,938 Great Britain NOV. 26, 1937 H B 488,792 France July 22, 1918 501,131 Great Britain Feb. 14, 1939 CHARLES F. H. ALLEN. 502,420 Great Britain Mar. 16, 1939 CHARLES V. WILSON. 514,093 Great Britain 1938 GORDON F. FRAME. 514,353 Great Britain 1938 Certificate of Correction Patent No. 2,448,853. September 7, 1948.

1: CHARLES F. H. ALLEN ET AL. 7

.It is hereby certified that error appears in the printed specification of the'above.

numbered patent requiring correction as follows: Column 14, line 39, for the word absence read presence; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 23rd day of November, A. D. 1948.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

